Utilization of 2-Nitro-6-(thiazol-2-yldiazenyl)

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ISSN 2291-6458 (Print), ISSN 2291-6466 (Online)
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Research Article
DOI:10.13179/canchemtrans.2014.02.03.0113
Utilization of 2-Nitro-6-(thiazol-2-yldiazenyl)phenol for
Spectrophotometric Determination of Trace Amounts of
Copper(II) in Water Samples
Alaa S. Amin,1,* Ragaa El-Sheikh,2 and Mohamed I. Shaltout2
1
Chemistry Department, Faculty of Science, Benha University, Benha, Egypt.
Chemistry Department, Faculty of Science, Zagazig University, Zagazig 44519, Egypt
2
*
Corresponding Author, E-mail: [email protected] Phone: +20552350996; Fax: +20132222578
Received: April 3, 2014 Revised: April 27, 2014 Accepted: April 27, 2014 Published: April 28, 2014
Abstract: A simple ultra sensitive and fairly selective non extractive spectrophotometric method for the
determination of copper using 2-nitro-6-(thiazol-2-yldiazenyl) phenol (NTDP) has been developed.. The
method is based on the color reaction of copper with NTDP at pH 7.1 buffer. The optimal reaction
conditions (e.g., reagent concentration, pH and effect of time and temperature) were studied and the
analytical characteristics of the method (e.g., limit of detection, limit of quantification, and linear ranges)
were obtained. Linearity was obeyed in the range of 0.1–5.0 µg/mL of copper(II) ion and the detection
limit of the method was 3.0 ng/mL. The relative standard deviation (RSD) and relative error for six
replicate measurements of 2.0 µg/mL Cu(II) were 0.76 % and 1.34 %, respectively. The interference
effect of some anions and cations was also tested. The method was applied to the determination of
copper(II) in water samples.
Keywords: Copper(II) determination; Spectrophotometry; Thiazolylazo compounds; Water analysis
1. INTRODUCTION
The essential trace elements are necessary for growth, normal physiological functioning, and
maintaining of life. However, the ingestion or inhalation of large dosesmaylead to toxic effects. Trace
metals are ubiquitous environmental contaminants and they can be easily taken up by humans, animals,
plants, and waters in the environment [1].
Copper is an essential nutrient for which World Health Organization (WHO) recommends a daily
intake of 30 mg per kg body weight [2]. Copper in drinking water can be an important source of dietary
copper for humans [3]. A major source of copper in drinking water is corrosion of copper pipes, which
can impart a taste to the water [4–6]. Copper in water may at times exceed health-based standards,
resulting in increased potential for flavour changes and health concerns [4–7]. Drinking water standards
have been established to prevent adverse health effects resulting from ingestion of too much copper.
WHO recommends a limit of 2.0 mg/L Cu(II) to prevent adverse health effects from copper exposure [2].
WHO guidelines also state that a long-term intake of copper between 1.5 and 3.0 mg/L has no adverse
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0.9
Cu-NTDP
0.8
NTDP
Absorbance
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
350 390 430 470 510 550 590 630
Wavelength (nm)
Figure 1. Absorption spectra of 2.0 µg/mL of Cu2+ complexed with NTDP at the optimum conditions.
health effects but greater levels than 5 mg/L in water can impart an undesirable bitter taste. The US
Environmental Protection Agency (USEPA) developed a health-based action level of 1.3 mg/L Cu in
drinking water [8] and an aesthetic-based standard of 1.0 mg/L Cu. Copper above this aesthetic standard
level can stain plumbing fixtures and laundry as well as contribute to metallic- or bitter-tasting water [9].
USEPA databases from 2003 [10] identified 471 drinking water systems in violation of the copper healthbased action level of 1.3 mg/L Cu. Recent problems with pinhole leaks (or nonuniform corrosion) in
copper pipes have raised awareness and concerns about an increase in copper levels in drinking water
[11].
Many techniques i.e. AAS [12], ICP-AES [13, 14], voltammetry [15], spectrophotometry [16]
have been reported for the determination of copper. AAS and ICP-AES are most selective and sensitive
techniques used for the determination of copper. These techniques, however, are quite expensive and
require costly maintenance and skilled hands for operation. Voltammetry is the most sensitive technique
but suffers from matrix interference [17,18]. Various organic and inorganic reagents viz. Phenols [19],
amines
[20–21],
carbazones
[22],
5-(4-sulphophenyl-azo)-8-aminoquinoline
[23],
5-(2benzothiazolylazo)-8-hydroxyquinolene [24], carbamates [25,26], oximate [27], thioamides [28,29],
carbonohydrazide [30] and azo [31–33] compounds have been proposed for the spectrophotometric
determination of copper at trace levels. These methods, however, are not entirely suitable due to the
involvement of one or more of the following reasons: the tedium involved in the methods, critical pH
ranges, poor sensitivity and the problem of matrix interference. Some other reagents like alizarin s-methyl
violet-poly(vinyl alcohol) system [34,35], 4-(2,3-dihydro-1,4-phthalazinedione-5-triazeno)-azobenzene
[36], 5-Br-PADAP [37], diphenyl-carbazide [38] have also been reported for the spectrophotometric
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determination of copper.
The present paper deals with a simple and sensitive method for the field identification and
spectrophotometric determination of copper in water samples using 2-nitro-6-(thiazol-2-yldiazenyl)
phenol (NTDP).
0.5
Absorbance
0.4
0.3
0.2
0.1
0
0
2
4
6
8
10 12
14
pH
Fig. 2. Effect of pH value on the complexationِ
Absorbance
of 2.0 / mL Cu(II) with 2.5 × 10−4 M NTDP
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
1
2
3
4
5
6
-4
[NTDP] x 10 M
Fig. 3. Effect of [NTDP] on the complexation
of 2.0 µg/mL of Cu(II) at pH 7.1.
2. MATERIALS AND METHODS
2.1. Apparatus
WTW digital pH-meter calibrated by standard buffer solutions before each measurement was
used. A Ceciel 7200S double beam UV–Visible spectrophotometer equipped with a quartz cell of 10 mm
path length was used for the absorption spectra and the absorbance measurements. The distilled modal
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Baby Steraline produced doubly distilled water. Temperature stabilization was obtained using water bath
model Memmert with a temperature range from ambient to 100 ºC.
2.2. Preparation of ligand
The ligand, 2-nitro-6-(thiazol-2-yldiazenyl)phenol (NTDP) was prepared according to the
procedure reported previously [39]. A solutions of 0.01 mole (10.013 g) of 2-aminothiazol [Sigma (St.
Loius, MO, USA)]; was prepared in 1:1 HCl and cooled to – 5.0 ºC. to this solution a cold sodium nitrite
solution of 0.01 mole (6.903 g) was added and mixed with stirring and kept in an ice bath of – 5.0 ºC for
20 min. The cooled diazonium salt solution was used for coupling with cold solution of 0.01 mole onitrophenol in 10 % NaOH. The azo compound formed was kept for 30 min in an ice bath of -5.0 ºC, then
filtered off, washed by water and dried. The crude material was recrystallized using dimethylformamide.
The chemical structure was confirmed by the elemental analysis, C, H, N, FTIR, and 1H-NMR spectra.
2.3. Chemicals and reagents
All chemicals used were of analytical reagent grade Sigma (St. Loius, MO, USA) and Merck
(Darmstadt, Germany). All solutions were prepared with distilled demineralized water. The stock standard
copper(II) solution was prepared by dissolving 0.6393 g of copper(II) chloride dehydrate in distilled water
and diluting to 250 mL. The solution was standardized titrimetrically by a known method [40]. The
method basically depends on the titration of evolving iodine in the presence of starch by the reduction of
Cu+2 to Cu+ in the mixtures containing iodide and copper(II) salts. The working standard solutions were
prepared by suitable dilution of the stock solution. Stock solution of NTDP was prepared by dissolving
appropriated weighed amounts of solid reagent in least amount of DMF and competed to the mark in a
100 mL measuring flask. Series of universal buffer solutions of pH = 2.56–12.41, were prepared by
following the standard methods [41].
2.4 General procedure
An aliquot of copper(II) standard solution was transferred to a 10 mL, 1.5 mL of the 2.5 mL of
10−3 M NTDP solution and 1.5 mL buffer solution of pH 7.1 were added. The solution was taken up to the
mark with bidistilled water and allowed to stand for 2.0 min in room temperature. The absorbance of the
solution was measured at 503 nm. The blank solution was submitted to the same procedure without
Cu(II).
2.5. Stoichiometric Relationship
The stoichiometric ratios of the complex formed between Cu2+ ion and NTDP was determined by
applying the continuous variation [42] and the molar ratio [43] methods at the wavelengths of maximum
absorbance. In continuous variation method, equimolar solutions were employed: 5.0 × 10−4 M standard
solutions of Cu2+ ion and 5.0 × 10−4 M solutions of NTDP were used. A series of solutions was prepared in
which the total volume of Cu2+ ion and NTDP was kept at 1.0 mL. The Cu2+ ion and NTDP were mixed in
various complementary proportions (0 : 1, 0.1 : 0.9, 0.2 : 0.8,. . ., 1 : 0, inclusive) and completed to
volume in a 10 mL calibrated flask as described in the above mentioned procedure. In the molar ratio
method, the concentrations of Cu2+ ion is kept constant (0.5 mL of 5.0 × 10−4 M) while that of and NTDP
(5.0 × 10−4 M) is regularly varied (0.1–1.4 mL). The absorbance of the prepared solutions is measured at
optimum condition complex.
3. RESULTS AND DISCUSSION
Complex of copper with NTDP in aqueous media has a maximum absorbance at 503 nm (Fig.
1). The absorption spectrum of the complex shows a maximum absorbance at 503 nm against a reagent
blank as the reference.
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Table 1. Tolerance ratios of diverse ions on the determination of 2.0 µg/mL of Cu(II)
Ion
K+, Na+
Ca2+, Mg2+
Br−
F−, Cl−, I−
SO42−, PO42−
Co2+, NO3−
Sr2+, Cr3+,
Ni2+, Citrate,
EDTA, Tartarate
Fe3+
Cu2+, Pb2+
Tolerance limit,
foreign/Cu (w/w)
15000
10000
7000
3000
2000
1250
900
400
200
15a
20
a
: after addition of ascorbic acid
Table 2. Analytical features of the proposed method
Parameters
Amount of DMF
pH
Optimum [NTDP]
Reaction time (min)
Stirring time (min)
Beer’s range (µg/ mL)
Ringbom range (µg/mL)
Molar absorptivity (L mol−1 cm−1)
Sandell sensitivity (ng cm−2)
Slope (µg/mL)
intercept
Correlation coefficient (r)
RSD a (%)
Detection limits (ng/mL)
Quantification limits (ng/mL)
b
Proposed method
0.5
7.1
2.5 × 10-4 M
2.0
10
0.1 – 5.0
0.25 – 4.75
7.07 × 104
1.82
5.5
- 0.004
0.9994
0.75
3.0
9.88
A = a + bC, where C is the concentration in µg/mL
and A is the absorbance units.
3.1. Optimization of the system
To take full advantage of the procedure, the reagent concentrations and reaction conditions must
be optimized. Various experimental parameters were studied in order to obtain optimum conditions. These
parameters were optimized by setting all parameters to be constant and optimizing one each time.
The effect of pH on the absorbance at a constant concentration of complex was investigated in the
range of 2.56–12.41. The absorbance of the Cu(II)– NTDP at 503 nm was studied against the reagent
blank. The absorbance was nearly constant in the pH range of 6.5–7.7. Therefore, pH 7.1 was selected as
optimal [Fig. 2]. Moreover the amount of pH 7.1 was studied to select the optimum volume. A 1.5–3.0
mL of pH 7.1 gave the highest absorbance value. Therefore 2.0 mL of pH 7.1 per 10 mL was selected for
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all further studies.
Effect of NTDP concentration on determination of copper was investigated in the range of 1.0–
5.0 × 10−4 M. The sensitivity of the method increased by increasing NTDP concentration up to 2.5 × 10−4
M [Fig. 3] and decreased at higher concentrations. It was expected that increasing NTDP causes an
increase in the absorbance of complex, because increasing in NTDP concentration caused an increase in
concentration of the complex. At concentrations higher than 2.5 × 10−4 M, the concentration of
uncomplexed NTDP increases significantly. Therefore, much probably decrease of absorbance change at
concentrations higher than 2.5 × 10−4 M is due to this fact that the free NTDP competes with the
complexes. A concentration of 2.5 × 10−4 M of NTDP was selected as the optimum.
Effect of time on the reaction procedure was investigated. The results showed that complexation
reaction was completed in 2.0 min. Raising the temperature upto 60 ºC has no effect on the complex
formation.
Table 3. Determination of copper in the water samples by the proposed and ICP-AAS methods
Sample
Tap water
Ground water
Seawater
Added
(µg/mL)
0.0
1.0
2.0
3.0
0.0
0.5
1.5
3.0
Copper founda (µg/mL)
proposed
ICP-AAS
1.1
1.11
2.15 ± 0.22
2.20 ± 0.52
3.05 ± 0.15
3.15 ± 0.38
4.20 ± 0.31
4.05 ± 0.43
1.5
1.95 ± 0.42
2.90 ± 0.27
4.55 ± 0.31
1.57
2.04 ± 0.63
3.03 ± 0.41
4.44 ± 0.36
t-valueb
F-testb
0.95
1.26
1.11
2.18
2.67
2.43
1.37
1.23
1.08
2.94
2.55
2.25
0.0
0.7
1.4
2.2
1.8
1.77
2.45 ± 0.19
2.53 ± 0.29
1.44
3.13
3.25 ± 0.44
3.31 ± 0.58
1.17
2.37
3.95 ± 0.30
4.07 ± 0.40
1.32
2.88
a
: Mean ± SD (n = 6).
b
The theoretical values of t- and F- at P = 0.05 are 2.571 and 5.05, respectively.
3.2. Stoichiometric Relationship Stability Constant
The stoichiometric ratio between Cu2+ ion and NTDP in the formed complex was determined by
the continuous variations and molar ratio methods. Job’s method of continuous variation of equimolar
solutions was employed: a 5.0 × 10−4 M standard solution of Cu2+ ion and NTDP, were used. A series of
solutions was prepared in which the total volume of Cu2+ ion and NTDP was kept at 1.0 mL. The
absorbance was measured at the optimum wavelength. The results indicate that 1 : 1 (Cu 2+ : NTDP)
complex is formed.
The stability of the complexes was evaluated. The formation of the complexes was rapid and the
orange color was stable at least for 12 h without any change in color intensity and with the maximum
absorbance at room temperature. The conditional stability constant of the complex was calculated from
the continuous variation data using the Harvey equation [44]. the conditional stability constant was found
to be 6.87.
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Table 4. Comparison of characteristic features of various spectrophotometric methods for the determination of
copper(II)
1-(2-Pyridylazo)-2-naphthol
λmax (nm) ε (L mol−1 Linear dynamic
cm−1)×105 range, µg/mL
595
–
0.5–3.6
Dithiocarbamate
434
0.13
4-(2`-benzothiazolylazo)salicylic acid
2,6-Dichlorophenolindo- phenol
Pyridylazo dye
Biacetyl-2-pyridylhydrazo nethylo-semicarbazone
N,N-diphenylbenzamidine
535
0.13
562
532
520
–
0.47
0.56
0.0544±0.0017 Poor sensitivity, Fe, Ni, Co, [26]
(DL)
interfere, critical pH
0.2–15
Poor sensitivity, Zn
[31]
interfere
5–300
V(IV), Cd(II) interfere
[19]
–
Less sensitivity
[34]
–
Fe, Co, Ni interfere
[24]
520
1.14
0.05–5.0
3-Thiobenzoyl-1-p-tolyl- thio- 420
carbamide
Naphthazarin
330
3-{2-[2-(2-hydroxyimino-1570
methyl-propylideneamino)ethylamino]-ethyl-imino}-butan2-one oxime
1,5-bis(di-2-pyridylmethyl -ene)- 420
thiocarbonohydrazide
NTDP
503
0.10
3–12
0.18
0.016
0.9–4.5
0.2–225
Fe(III), Al(III), Cr interfere [46]
Sensitive and selective,
[25]
Ni(II) interfere except
access reagent total
0.42
0.1–1.3
0.707
0.1–5.0
Co(II), Ni(II), Fe(III), Hg(I), [30]
Hg(II) interfere
Fe(III), interfere
P.M
Reagents
Remarks
Ref.
Many metals interfere
[32]
Sensitive and selective, Zn, Cd [21]
interfere
Poor sensitivity
[29]
P.M. Proposed method
3.3. Selectivity
The effect of different cations and anions on the determination of 2.0 µg/ mL copper by the
proposed method was studied. An ion was considered to be an interferent when it caused a variation
greater than ± 5.0 % in the absorbance of the sample. For the determination of 2.0 µg/mL Cu(II) by this
method, the foreign ions can be tolerated at the levels given in Table 1. NTDP forms stable complexes
with various metal ions, including transition metal ions. Most of the cations and anions examined do not
interfere with the determination of Cu(II). Fe(III) interfered at 1.0 µg/mL. The interfering effects of
Fe(III) up to 15.0 µg mL−1, were completely removed by the addition of 5.0×10−4 M ascorbic acid to the
solution.
3.4. Analytical characteristics
Table 2 summarizes the analytical characteristics of the optimized method, including regression
equation, linear range and limit of detection, and reproducibility. The limit of detection, defined as CL
=3SB/m (where CL, SB, and m are the limit of detection, standard deviation of the blank and slope of the
calibration graph, respectively), was 3.0 ng/mL. The relative standard deviation (RSD) and relative error
for six replicate measurements of 2.0 µg/mL of copper was 0.76% and 1.34% and for 4.0 ng/mL of
copper was 1.27% and 1.02%, respectively.
3.5. Analytical applications
Aiming to demonstrate the usefulness of the proposed system a set of samples comprising several
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water samples was analyzed. The system was run using the optimized parameters summarized in Table 2.
The results of sample are shown in Table 3. Accuracy was assessed by comparing results with these
obtained using inductive coupled plasma atomic absorption spectrometry (ICP–AAS). The recoveries are
close to 100% and indicate the proposed method was helpful for the determination of copper in the real
samples. Applying the paired t- and F-test [45] no significant difference at 95% confidence level was
observed.
4. CONCLUSION
The proposed procedure gives a simple, very sensitive and low-cost spectrophotometric
procedure for determination of copper ion that can be applied to water samples. A comparison between
the proposed method with the previously reported methods for determination of copper (Table 4)
indicates that this method has a lower detection limit, wider linear range and is a convenient, safe, simple,
rapid and inexpensive method for the determination of trace quantities of copper to water samples.
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The authors declare no conflict of interest
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